JPH07242583A - Dialdehyde compound and germicide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain the subject compound effectively usable as an agricultural and horticultural germicide against disease injuries such as Pyricularia oryzae and Cochliobolus miyabeanus of rice plant and Erysiphe graminis f. sp. hordei or Erysiphe graminis f. sp. tritici, Gibberella zeae or Puccinia striiformis, Puccinia graminis, Puccinia recondita or Puccinia hordei of barleys or wheats. CONSTITUTION:This 3-formyl-7,11-dimethyl-(2E,6Z,10)-dodecatrien-1-al (a dialdehyde compound) is expressed by the formula. The compound is obtained by extracting a liquid component secreted from a mandibular gland in the head part of Lasius fuliginosus Latreille with an organic solvent or can further be obtained by the organic synthesis. The compound expressed by the formula is directly used as an active ingredient or diluted with water for use. The compound is useful for controlling plant disease injuries in a paddy field, a farmland, an orchard, a tea field, a pasture, a turf, etc., and further as a slime controlling agent for papermaking, an industrial germicide for pigments, leathers, building materials, adhesives, plastics, etc. The compound expressed by the formula as the active ingredient in an amount of 0.1-99.9wt.%, preferably 1-99wt.% is contained in the germicide.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a dialdehyde compound and a fungicide containing the same as an active ingredient.

[0002]

DETAILED DESCRIPTION OF THE INVENTION The present inventors have conducted intensive studies on an extract of an ingredient secreted from the maxillary gland of a black ant with an organic solvent, and as a result, found that the extract has bactericidal activity. In the course of separating and purifying the compound, the presence of a dialdehyde compound represented by the following formula 2 as the component was confirmed, and it was found that the compound has an excellent bactericidal activity. That is, the present invention is represented by Formula 2

[Chemical 2] A dialdehyde compound (chemical name: 3-formyl-7,11-dimethyl- (2E, 6Z, 10) -dodecatrien-1-al; hereinafter referred to as the compound of the present invention)
And a fungicide containing the same as an active ingredient.

The compound of the present invention is a black ant Lasius ful.
The liquid component secreted from the maxillary gland of the head of iginosus Latreille can be obtained by an ordinary natural product chemistry method, that is, an organic solvent extraction, an isolation operation by silica gel chromatography and the like. The compound of the present invention can also be obtained by organic synthesis.

The compound of the present invention can be used as an active ingredient of a fungicide for agricultural and horticultural use, and a plant disease for which the compound of the present invention is effective is rice blast (Pyricularia oryz).
ae), sesame leaf blight (Cochliobolus miyabeanus), blight
(Rhizoctonia solani), powdery mildew of wheat (Erysiph
e graminis f. sp. hordei, f. sp. tritici), Fusarium head blight (Gibberella zeae), Rust (Puccinia striiformi)
s, P. graminis, P. recondita, P. hordei), snow rot
(Typhula sp., Micronectriella nivalis), naked smut
(Ustilago tritici, U. nuda), Eyespot (Pseudoc
ercosporella herpotrichoides), cloud disease (Rhynchospor
ium secalis), leaf blight (Septoria tritici), wilt disease
(Leptosphaeria nodorum), black spot of citrus (Diaport
he citri), scab (Elsinoe fawcetti), fruit rot (Penicillium digitatum, P. italicum), apple monili (Sclerotinia mali), rot (Valsa ma)
li), powdery mildew (Podosphaera leucotricha), leaf spot disease (Alternaria mali), scab (Venturia inaequali)
s), pear scab (Venturia nashicola), black spot (Al)
ternaria kikuchiana), scab (Gymnosporangium hara)
eanum), peach scab (Sclerotinia cinerea), scab
(Cladosporium carpophilum), Phomopsis rot (P
homopsis sp.), black wilt of grape (Elsinoe ampelina)
, Late rot (Glomerella cingulate), powdery mildew (Unc
inula necator), rust (Phakopsora ampelopsidis),
Oyster anthracnose (Gloeosporium kaki), leaf rot (Cercospo)
ra kaki, Mycosphaerella nawae), anthracnose of cucumber (Co
lletotrichum lagenarium), powdery mildew (Sphaerotheca
fuliginea), vine blight (Mycosphaerella melonis),
Tomato ring spot (Alternaria solani), leaf mold (Clad
osporium fulvum), brown leaf spot of eggplant (Phomopsis vexans)
, Powdery mildew (Erysiphe cichoracearum), black spot of cruciferous vegetables (Alternaria japonica), white spot (Cerc)
osporella brassicae), rust onion (Puccinia alli)
i), soybean purpura (Cercospora kikuchii), black scab (Elsinoe glycines), black spot (Diaporthe phaseolo)
rum var. sajae), anthracnose of green beans (Colletotrichum)
lindemuthianum), peanut black scab (Mycosphaerell)
a personnatum), brown spot (Cercospora arachidicol)
a), powdery mildew of pea (Erysiphe pisi), summer blight of potato (Alternaria solani), powdery mildew of strawberry
(Sphaerotheca humuli), tea leaf blast (Exobasidiu)
m reticulatum), white scab (Elsinoe leucospila), tobacco scab (Alternaria longipes), powdery mildew (Erys)
iphe cichoracearum), anthracnose (Colletotrichum tabac
um), brown spot of sugar beet (Cercospora beticola), scab of rose (Diplocarpon rosae), powdery mildew (Sphaerot)
heca pannosa), brown spot on chrysanthemum (Septoria chrysanthem)
i-indici), white rust (Puccinia horiana), gray mold of various crops (Botrytis cinerea), sclerot (Sclerot)
inia sclerotiorum), and the like. Furthermore, the compound of the present invention can be used as an active ingredient of fungicides other than those for agricultural and horticultural use, and examples of bacteria (microorganisms) which can be controlled by the compound of the present invention include the following. Bacteria Bacillus, Clostoridium, Enterococcus, Flavob
Acterium, Klebsiella, Micrococcus, Proteus
Genus, Pseudomonas genus yeasts Candida genus, Saccharomyces genus fungi Alternaria genus, Aspergillus genus, Penicillium genus, Chae
tomium, Cladosporium, Aureobasidium, Tyromy
ces, Coriolus, Myrothecium, Fusarium

When the compound of the present invention is used as an active ingredient of an agricultural and horticultural fungicide, that is, a plant disease controlling agent, it may be used as it is without adding any other ingredients, but it is usually a solid carrier, liquid carrier or surfactant. Mixed with other formulation aids,
It is used by formulating into emulsion, wettable powder, suspension, granule, powder, liquid and the like. These formulations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99.9%, preferably 1 to 99%. As a solid carrier, kaolin clay, attapulgite clay, bentonite, acid clay, bilophyllite, talc, diatomaceous earth, calcite, walnut powder, urea,
Fine powder or granules such as ammonium sulfate and synthetic hydrous silicon oxide may be mentioned, and examples of the liquid carrier include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol and cellosolve,
Ketones such as acetone, cyclohexanone, and isophorone,
Soybean oil, vegetable oils such as cottonseed oil, dimethyl sulfoxide, acetonitrile, water and the like, and as the surfactant used for emulsification, dispersion, wet extension, etc., alkyl sulfate ester salts, alkyl (aryl) sulfonates, Anionic surfactant such as dialkyl sulfosuccinate, polyoxyethylene alkylaryl ether phosphate ester salt, polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, poly Examples thereof include nonionic surfactants such as oxyethylene sorbitan fatty acid ester. As a formulation auxiliary agent, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(Carboxymethyl cellulose), PAP (acidic isopropyl phosphate) and the like.

[0006] These formulations are sprayed as they are or diluted with water for foliage application, or they are dusted and dispersed in soil to mix them, or they are applied to the soil, or they are dispersed and applied to the surface of the water. Used in the form of. In addition, when used in combination with other plant disease controlling agents, it can be expected to enhance the controlling effect. Further, it can be used in combination with an insecticide, an acaricide, a nematicide, a herbicide, a plant growth regulator, a fertilizer or a soil conditioner. The compound of the present invention can be used as an active ingredient of a plant disease controlling agent for paddy fields, upland fields, orchards, tea fields, meadows, lawns and the like. When the compound of the present invention is used as an active ingredient of a plant disease controlling agent, its application amount is usually 0.05 g to 100 g, preferably 0.1 g to 20 g per are, and an emulsion, a wettable powder, a suspension, a liquid preparation. When diluted with water and applied, the application concentration is 0.0005% to 1%, preferably 0.001% to 0.2%, and granules, powders, etc. are applied as they are without any dilution.

When the compound of the present invention is used as a fungicide other than agricultural and horticultural use, its use is not necessarily limited as long as it is desired to impart antimicrobial activity. For example, textiles, leather, building materials, wood, paints, Adhesive, plastic,
Examples include films, papers, optical devices, pharmaceuticals, cosmetics, other industrial products such as automobiles and electronic industrial products, and their parts, protection of materials, and sterilization hygiene of environments such as factories and homes. When the compound of the present invention is used as an active ingredient of an industrial bactericide, it can take any form or use form that can be adopted as an industrial bactericide. Specifically, the compound of the present invention is used as it is, or after being diluted with water, an organic solvent, a solid powder or another suitable carrier, or is generally used for the production of an industrial bactericide. Depending on the method used, various liquid or solid carriers may be mixed, and if necessary, auxiliary agents such as wetting agents, dispersants, emulsifiers, adhesives, lubricants, etc. may be added to prepare wettable powders, liquid preparations, emulsions, powders and granules. It can be used in various dosage forms such as an agent and a fine granule. In these formulations, the compound of the present invention is used as an active ingredient in a weight ratio of 0.1.
.About.99.9%, preferably 1 to 99%. In the production of these preparations, as the liquid carrier, those which serve as a solvent for the compound of the present invention or those which can be dispersed or dissolved by an auxiliary agent are used. For example, water,
Examples include methanol and dimethyl sulfoxide. As a solid carrier, silica gel, diatomaceous earth, alumina,
Examples include talc, calcium carbonate, clay and the like. Examples of the auxiliary agent include acetone and hexane.

The industrial bactericidal agent of the present invention is not necessarily limited as long as it is applied to microorganisms and bacteria to be controlled, but for example, a slime formation inhibitor (slime control agent) in a cooling water system or a paper mill, a pigment, It can be used as an antibacterial agent for cutting oil, leather, building materials, adhesives, plastics and the like. When the compound of the present invention is used as an active ingredient of an industrial fungicide, the concentration used depends on the properties of the microorganisms and bacteria to be controlled, the composition of the material to be protected and the like. The optimum amount to be used can be determined by systematic testing. Generally, the suitable concentration is in the range of 0.01 ppm to 100000 ppm based on the weight of the material to be protected, and when used as a slime control agent for papermaking, it is preferably in the range of 0.05 ppm to 100000 ppm.

[0009]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. First,
Examples of compound extraction and isolation are shown below. Extraction and isolation example The heads of 400 black ant L. fuliginosus were n-
It was immersed in 40 ml of hexane and left overnight at room temperature. next,
After filtering the n-hexane solution, the filtrate was concentrated under reduced pressure, and the solvent was completely distilled off to obtain 420 mg of a pale yellow viscous oil (hereinafter, referred to as a crude extract). The crude extract was subjected to silica gel chromatography by the method described below. A cylindrical glass column having an inner diameter of 2.7 cm and a height of 50 cm was packed with 15 g of silica gel by a wet method using n-hexane, and 0.420 g of the crude extract was placed on the upper end of the silica gel.
-Elution of the components was sequentially started with -hexane and then with a mixed solvent of n-hexane and diethyl ether. The solvent of the fraction eluted with a 9: 1 mixed solvent of n-hexane and diethyl ether was distilled off to obtain 0.280 g of an oily substance. The obtained oily substance was subjected to silica gel thin layer chromatography using a mixed solvent of n-hexane and ethyl acetate at 70:30 as a developing solvent, and the compound of the present invention having an Rf value of 0.65.
g was obtained.

The properties and spectral data thereof are shown below. Appearance: Light yellow oil UV (1,4-dioxane) λmax: 233.6 nm (ε: 15
385.5) MS m / z: EIM ⁺ 234 (0.6), 219 (0.6), 216
(1.2), 205 (0.9), 201 (1.5), 191 (3.3), 173 (2.5), 1
65 (8.5), 147 (6.0), 136 (9.1), 69 (100): CI MH ⁺ 235 (70), 217 (100) ¹ H-NMR (CDCl _{3 /} TMS) δ (ppm): 1.510
(S, 3H), 1.587 (s, 3H), 1.669 (s, 3)
H), 2.000 (m, 4H), 2.207 (q, 2H), 2.72
1 (t, 2H, J = 7.2Hz), 5.100 (m, 2H), 6.
550 (d, 1H, J = 7.5Hz), 9.664 (s, 1H),
10.205 (d, 1H, J = 7.5Hz) ¹³ C-NMR (CDCl ₃ / TMS) In addition, s, d, t, and q below show the division pattern under off-resonance conditions. δc (ppm) OFR INEPT 16.089 (q) CH ₃ / CH 17.606 (q) CH ₃ / CH 23.999 (t) CH ₂ / C 25.570 (q) CH ₃ / CH 26.491 (t) CH ₂ / C 27.412 (t) CH ₂ / C 39.547 (t) CH ₂ / C 121.459 (d) CH / CH ₃ 124.005 (d) CH / CH ₃ 131.535 (s) C / CH ₂ 138.415 (s) C / CH ₂ 140.962 (d) CH / CH ₃ 154.234 (s) C / CH ₂ 191.127 (d) 194.865 (d)

Next, formulation examples are shown. In addition, parts represent parts by weight. Formulation Example 1 50 parts of the compound of the present invention, calcium lignin sulfonate 3
Parts, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain a wettable powder. Formulation Example 2 An emulsion is obtained by thoroughly mixing 10 parts of the compound of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 70 parts of xylene. Formulation Example 3 2 parts of the compound of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed, and water is added and kneaded well, and then granulated and dried. To obtain granules. Formulation Example 4 25 parts of the compound of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed and wet-milled until the particle size of the active ingredient becomes 5 microns or less to obtain a suspension agent. Formulation Example 5 10 parts of the compound of the present invention, 1 part of polyoxyethylene styryl phenyl ether and 89 parts of water are mixed to obtain a liquid preparation.

Next, it is shown in Test Examples that the compound of the present invention is useful as an active ingredient of a fungicide. Test Example 1 Wheat powdery mildew control test (therapeutic effect) A plastic pot was filled with sandy loam, and wheat (Agriculture 73
No.) was sowed and grown in a greenhouse for 10 days. The wheat seedlings developed by the second leaf were sprinkled with spores of wheat powdery mildew and inoculated. After inoculation, the seedlings were grown in a greenhouse at 23 ° C for 3 days, and the compound of the present invention made into a wettable powder according to Formulation Example 1 was diluted with water to a concentration of 500 ppm so that it could be sufficiently attached to the leaf surface of the wheat seedling. Foliage was sprayed on. After spraying, 23 ℃
Was grown in a greenhouse for 6 days and the control efficacy was investigated. as a result,
In the wheat treated with the compound of the present invention, powdery mildew did not develop at all.

Test Example 2 Antifungal test 50 pp of the compound of the present invention dissolved in dimethyl sulfoxide
Potato sap agar (PP
Mix in A). After that, inoculate the test bacteria, and 5 at 27 degrees
Cultured for a day. After culturing, the growth of the fungus was investigated. The antifungal activity is "5" if the growth of the bacteria at the time of the survey is visually observed, "4" if the growth of the bacteria is not observed at all, and "3" if the growth of the bacteria is observed at about 30%. "2" if about 50% is recognized, "1" if about 70% is recognized, and "0" if there is no difference with the growth of the bacteria when the compound is not tested above, 6 levels And evaluated as 5, 4, 3, 2, 1, 0, respectively.

[Table 1] Test bacterium a: Alternaria alternata b: Aspergillus niger apple pathotype c: Aureobasidium pullulans d: Cladosporium e: Penicillium funiculosum cladosporioides f: Chaetomium globosum g: Fusararium oxysporum f. Sp. Lycopersici

[0014]

The compound of the present invention exhibits excellent bactericidal activity.

Claims (2)

[Claims] 1. Formula 1 A dialdehyde compound represented by. 2. A bactericide containing the dialdehyde compound according to claim 1 as an active ingredient.